a pale yellow oil [Rf = 0.23 (1 : 2 hexanes : EtOAc)]; IR mmax/cm−1
N-(2-Aziridin-1-yl-1-ethyl-heptyl)-4-methyl-benzenesulfonamide
(25b)
=
3329 (N–H), 2967–2875 (C–H), 1598 (N–H), 1333 (S O), 1159
=
(S O), 1092 (C–N); dH (CDCl3) 0.72 (3H, t, J 7.5, CH2CH3),
Synthesised in a similar manner to 14, diamine 21b (207 mg,
0.581 mmol) gave a 25 : 75 mixture of piperazine 24b and
aziridine 25b with the reaction byproducts PPh3O and diethyl
hydrazidodicarboxylate. Chromatography (silica) gave aziridine
25b (26 mg, 0.077 mmol) as a 1 : 1 mixture with diethyl
hydrazidodicarboxylate as a yellow oil [Rf = 0.20 (1 : 1 hexanes :
EtOAc)], further purification by chromatography (alumina) led
to degradation of the substrate, IR mmax/cm−1 3296 (N–H), 2956–
1.16 (1H, dqd, J 14.4, 7.4, 4.6, CH2CH3), 1.27 (1H, b, NH),
1.68 (1H, ddq, J 14.4, 10.0, 7.5, CH2CH3), 2.43 (3H, s, ArCH3),
2.68 (1H, td, J 12.4, 3.6, CH2N), 2.90 (1H, ddd, J 12.2, 3.2, 1.3,
CH2N), 3.14 (1H, ddd, J 15.8, 12.6, 3.2, CH2N), 3.73 (1H, ddt,
J 14.2, 3.4, 1.3, CH2N), 3.89 (1H, d, J 3.6, FurCHN), 3.89 (1H,
dt, J 9.9, 4.0, CHNTs), 6.12 (1H, dt, J 3.3, 1.0, FurH), 6.31
(1H, dd, J 3.2, 1.9, FurH), 7.30–7.36 (3H, m, FurH, ArH), 7.78
(2H, d, J 8.3, ArH); dC (CDCl3) 10.6 (CH3), 17.6 (CH2), 21.6
(CH3), 40.5 (CH2), 45.2 (CH2), 56.4 (CH), 58.0 (CH), 105.6 (CH),
111.2 (CH), 127.1 (CH), 129.8 (CH), 139.0 (Cq), 141.6 (CH), 143.2
(Cq), 154 (Cq); m/z 335.1420 (MH+, 100%, C17H22N2O3S requires
335.1429).
=
=
2858 (C–H), 1599 (N–H), 1330 (S O), 1160 (S O), 1093 (C–
N); dH (CDCl3) 0.80 (3H, t, J 7.4, CHCH2CH3), 0.85 (3H, t,
J 7.3, CH2CH2CH3), 0.95–1.77 (14H, m, CH2), 2.42 (3H, s,
ArCH3), 2.42–2.45, CHNH), 3.19 (1H, q, J 7.6, CHNTs), 5.32
(1H, d, J 7.7, NH), 7.29 (2H, d, J 8.8, ArH), 7.77 (2H, d,
J 8.2, ArH); dC (CDCl3) 10.1 (CH3), 14.2 (CH3), 14.5 (CH3),
22.7 (CH2), 24.8 (CH2), 26.2 (CH2), 26.5 (CH2), 28.0 (CH2), 31.5
(CH2), 32.1 (CH2), 57.8 (CH), 69.9 (CH), 127.0 (CH), 129.5 (CH),
138.8 (Cq); m/z 339.2089 (MH+, 100%, C18H31N2O2S, requires
339.2106).
N-{1-[Aziridin-1-yl-(furan-2-yl)-methyl]-propyl}-4-methyl-
benzenesulfonamide (25a)
Synthesised in a similar manner to 14, diamine 21a (45 mg,
0.13 mmol) gave, after chromatography, a 65 : 35 mixture of
aziridine 25a and piperazine 24a (33 mg, 0.098 mmol, 76%) as a
yellow oil which could be separated by chromatography (alumina)
to give aziridine 25a (21 mg, 0.062 mmol, 48%) [Rf = 0.23 (1 : 2
hexanes : EtOAc)]; IR mmax/cm−1 3293 (N–H), 3062–2876 (C–H),
4-Methyl-N-{1-[(2-methyl-aziridin-1-yl)-phenyl-methyl]-propyl}-
benzenesulfonamide (25c)
=
=
1599 (N–H), 1320 (S O), 1161 (S O), 1093 (C–N); dH (CDCl3)
0.73 (3H, t, J 7.5, CH2CH3), 1.15 (1H, dd, J 7.2, 4.2, CH2N),
1.22 (1H, dd, J 7.2, 4.1, CH2N), 1.37–1.47 (2H, m, CH2CH3),
1.60–1.67 (2H, m, CH2N), 2.43 (3H, s, ArCH3), 2.63 (1H, d, J
3.6, FurCHN), 3.41 (1H, qd, J 6.9, 3.7, CHNTs), 5.03 (1H, d, J
6.5, NH), 6.25 (1H, dt, J 3.2, 0.7, FurH), 6.33 (1H, dd, J 3.2, 1.9,
FurH), 7.28–7.31 (2H, m, ArH), 7.37 (1H, dd, J 1.9, 0.9, FurH),
7.81 (2H, d, J 6.5, ArH); dC (CDCl3) 10.4 (CH3), 21.6 (CH3), 24.9
(CH2), 26.1 (CH2), 28.3 (CH2), 58.7 (CH), 69.3 (CH), 108.3 (CH),
110.1 (CH), 127.5 (CH), 129.5 (CH), 137.8 (Cq), 142.4 (CH), 143.1
(Cq), 152.5 (Cq); m/z (EI+) 335.1417 (MH+, 100%, C19H25N2O2S
requires 335.1429), 292 (63).
Synthesised in a similar manner to 13 or 14, diamine 21c (104 mg,
0.277 mmol) gave aziridine 25c (34 mg, 0.094 mmol, 34%) [Rf =
0.48 (1 : 2 hexanes : EtOAc)]; IR mmax/cm−1 3293 (N–H), 3100–
=
=
2875 (C–H), 1322 (S O), 1160 (S O), 1093 (C–N); dH (CDCl3)
0.76 (3H, t, J 7.4, CH2CH3), 1.03 (3H, d, J 5.4, CHCH3), 1.21–
1.52 (4H, m, CH2CH3/2 × CH2N/CHCH3), 1.55–1.64 (1H, m,
CH2CH3), 2.46 (3H, s, ArCH3), 2.69 (1H, d, J 3.4, CHPh), 3.35–
3.43 (1H, m, CHNTs), 4.71 (1H, d, J 7.7, NH), 7.28–7.39 (7H, m,
ArH), 7.83 (2H, d, J 8.3, ArH); dC (CDCl3) 10.6 (CH3), 18.0 (CH3),
21.4 (CH3), 23.7 (CH2), 32.5 (CH), 36.6 (CH2), 60.7 (CH), 75.9
(CH), 127.3 (CH), 128.0 (CH), 128.2 (CH), 129.4 (CH), 138.2 (Cq),
140.0 (Cq), 143.0 (Cq); m/z 359.1792 (MH+, 100%, C20H27N2O2S
requires 359.1788).
2-Ethyl-3-pentyl-1-(toluene-4-sulfonyl)-piperazine (24b)
Synthesised in a similar manner to 13, diamine 21b (207 mg,
0.581 mmol) gave a 75 : 25 mixture of piperazine 24b and
aziridine 25b (142 mg, 72%) as a yellow oil which could be
separated by chromatography (silica) to give piperazine 24b
(100 mg, 0.292 mmol, 50%) as a yellow oil [Rf = 0.17 (1 : 1
hexanes : EtOAc)]; IR mmax/cm−1 3300 (N–H), 2957–2872 (C–
2-Ethyl-3-phenyl-1-(toluene-4-sulfonyl)-1,4-diazepane (24d)
Synthesised in a similar manner to 13, diamine 21d (100 mg,
0.270 mmol) gave 1,4-diazepane 24d (69 mg, 0.191 mmol, 71%) as
a pale yellow oil [Rf = 0.41 (2 : 1 hexanes : EtOAc)]; IR mmax/cm−1
=
3340 (N–H), 3061–2876 (C–H), 1598 (N–H), 1332 (S O), 1155
=
=
=
H), 1343 (S O), 1154 (S O), 1091 (C–N); dH 0.89 (3H, t, J
7.2, CH2CH2CH3), 0.90 (3H, t, J 7.4, CHCH2CH3), 1.14–1.33
(8H, m, CH2), 1.40 (1H, dqd, J 14.3, 7.4, 4.2, CHCH2CH3), 1.70
(1H, ddq, J 14.4, 10.9, 7.0, CHCH2CH3), 2.42 (3H, s, ArCH3),
2.49–2.54 (1H, m, CHNH), 2.54 (1H, td, J 12.4, 3.5, CH2N),
2.75 (1H, dd, J 12.2, 2.0, CH2N), 3.05 (1H, ddd, J 14.4, 12.7,
3.2, CH2N), 3.62–3.67 (1H, m, CH2N), 3.74 (1H, dt, J 7.2, 3.7,
CHNTs), 7.28 (2H, d, J 8.4, ArH), 7.72 (2H, d, J 8.3, ArH); dC
(CDCl3) 10.7 (CH3), 14.1 (CH3), 16.2 (CH2), 21.5 (CH3), 22.5
(CH2), 25.6 (CH2), 31.9 (CH2), 33.0 (CH2), 40.9 (CH2), 45.4
(CH2), 57.7 (CH), 58.1 (CH), 127.0 (CH), 129.7 (CH), 139.3
(Cq), 142.9 (Cq); m/z 339.2085 (MH+, 100%, C18H30N2O2S requires
339.2106).
(S O), 1089 (C–N); dH (CDCl3) 0.31 (3H, t, J 7.4, CH2CH3),
1.14 (1H, dqd, J 14.8, 7.5, 4.1, CH2CH3), 1.58 (1H, ddq, J 14.8,
11.2, 7.4, CH2CH3), 1.77–1.92 (1H, m, CH2CH2N), 2.05–2.14
(1H, m, CH2CH2N), 2.41 (3H, s, ArCH3), 2.84 (1H, ddd, J 13.6,
10.7, 4.6, CH2NTs), 3.11 (1H, ddd, J 14.8, 7.0, 6.8, CH2NH),
3.23 (1H, ddd, J 13.6, 6.1, 3.5, CH2NTs), 3.78 (1H, ddd, J 14.9,
7.9, 4.3, CH2NH), 3.96 (1H, dt, J 11.2, 3.6, CHNTs), 4.10 (1H,
d, J 3.2, PhCHN), 7.22–7.35 (7H, m, ArH), 7.77 (2H, d, J 8.2,
ArH); dC (CDCl3) 10.8 (CH3), 17.1 (CH2), 21.5 (CH3), 30.6 (CH2),
40.1 (CH2), 47.5 (CH2), 64.6 (CH), 70.6 (CH), 126.8 (CH), 127.1
(CH), 128.4 (CH), 129.5 (CH), 138.6 (Cq), 142.0 (Cq), 142.9 (Cq);
m/z (EI+) 359.1788 (MH+, 100% C20H26N2O2S requires 359.1793),
212 (12).
This journal is
The Royal Society of Chemistry 2007
Org. Biomol. Chem., 2007, 5, 2413–2422 | 2421
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